Copper-catalyzed hydrostannation of activated alkynes

[reactions: see text] [(Ph3P)CuH]6 effectively catalyzes the hydrostannation of activated alkynes with exclusive regioselectivity for alpha-stannation. Syn hydrostannation is observed exclusively for alkynoates. Anti or syn hydrostannation adducts are obtained as products for alkynone substrates.     

Comparison of microemulsion electrokinetic chromatography and micellar electrokinetic chromatography methods for the analysis of phenolic compounds

In this study, microemulsion electrokinetic chromatography (MEEKC) and micellar electrokinetic chromatography (MEKC) were compared for their abilities to separate and detect thirteen phenolic compounds (syringic acid, p-coumaric acid, vanillic acid, caffeic acid, gallic acid, 3,4-dihydroxybenzoic acid, 4-hydroxybenzoic acid, (+)-catechin, (-)-epigallocatechin, (-)-epicatechin gallate, (-)-epigallocatechin gallate, (-)-epicatechin, and (-)-gallocatechin), and two other ingredients (caffeine and theophylline) in teas and grapes. Separation of phenolic compounds was improved by changing the SDS concentration for MEEKC, but the SDS concentration rarely affected the resolution for MEKC. Organic modifier (acetonitrile or methanol) was found to markedly influence the resolution and selectivity for both MEEKC and MEKC systems. In addition, a higher voltage and a higher column temperature improved the separation efficiency without any noticeable reduction in resolution for MEEKC whereas they caused a poor resolution for the MEKC system. Although separations with baseline resolution were achieved by the optimized MEEKC and MEKC methods, the separation selectivity resulting from the proposed MEEKC method was completely different from that of MEKC.     

Azapeptide activity-based probes for the SARS-CoV-2 main protease enable visualization of inhibition in infected cells

The COVID-19 pandemic has revealed the vulnerability of the modern, global society. With expected waves of future infections by SARS-CoV-2, treatment options for infected individuals will be crucial in order to decrease mortality and hospitalizations. The SARS-CoV-2 main protease is a validated drug target, for which the first inhibitor has been approved for use in patients. To facilitate future work on this drug target, we designed a solid-phase synthesis route towards azapeptide activity-based probes that are capped with a cysteine-reactive electrophile for covalent modification of the active site of M^pro. This design led to the most potent ABP for M^pro and one of the most potent inhibitors reported thus far. We demonstrate that this ABP can be used to visualize M^pro activity and target engagement by drugs in infected cells.

The COVID-19 pandemic has revealed the vulnerability of the modern, global society.     

Cryptanalysis and Improvement in Multi-Party Quantum Key Distribution Protocol with New Bell States Encoding Mode

International Journal of Theoretical Physics - Ma et al. [Int. J. Theor. Phys. (2021): 1328–1338] proposed a multi-party quantum key distribution (MQKD) protocol using Bell states, in which...     

A Novel Route to the Fused Maleic Anhydride Moiety of CP Molecules

A seven‐step cascade reaction —in which selective mesylation, epoxide formation, epoxide lysis, cyclization, reiterative oxidation, and nitrogen–oxygen exchange occur sequentially—facilitates the construction of the maleic anhydride moiety of CP molecules 1 and 2 (>93% yield per step). Unstable intermediates of this reaction sequence were detected, providing evidence for the proposed mechanism and resulting in the discovery of a new chemical entity.     

Diterpenoid Compounds Isolated from Chloranthus oldhamii Solms Exert Anti-Inflammatory Effects by Inhibiting the IKK/NF-κB Pathway

Chloranthus oldhamii Solms (CO) is a folk medicine for treating infection and arthritis pain but its pharmacological activity and bioactive compounds remain mostly uncharacterized. In this study, the anti-inflammatory compounds of C. oldhamii were identified using an LPS-stimulated, NF-κB-responsive RAW 264.7 macrophage reporter line. Three diterpenoid compounds, 3α-hydroxy-ent-abieta-8,11,13-triene (CO-9), 3α, 7β-dihydroxy-ent-abieta-8,11,13-triene (CO-10), and decandrin B (CO-15) were found to inhibit NF-κB activity at nontoxic concentrations. Moreover, CO-9 and CO-10 suppressed the expression of IL-6 and TNF-α in LPS-stimulated RAW 264.7 cells. The inhibitory effect of CO-9 on TNF-α and IL-6 expression was further demonstrated using LPS-treated bone marrow-derived macrophages. Furthermore, CO-9, CO-10, and CO-15 suppressed LPS-triggered COX-2 expression and downstream PGE2 production in RAW 264.7 cells. CO-9 and CO-10 also reduced LPS-triggered iNOS expression and nitrogen oxide production in RAW 264.7 cells. The anti-inflammatory mechanism of the most effective compound, CO-9, was further investigated. CO-9 attenuated LPS-induced NF-κB activation by reducing the phosphorylation of IKKα/β (Ser176/180), IκBα (Ser32), and p65 (Ser534). Conversely, CO-9 did not affect the LPS-induced activation of MAPK signaling pathways. In summary, this study revealed new anti-inflammatory diterpenoid compounds from C. oldhamii and demonstrated that the IKK-mediated NK-κB pathway is the major target of these compounds.     

Simultaneous determination of Co(II), Cr(VI), Ni(II) and Pb(II) in water by solvent extraction and high-field 1H NMR Spectrometry

A novel analytical approach is described that combines the preconcentration power of solvent extraction with the resolution and sensitivity of a 500 MHz ¹H NMR spectroscopic detection method for the quantitative determination of metals. Co(II), Cr(VI), Ni(II) and Pb(II) in water are extracted into chloroform as dithiocarbamate complexes. By decoupling the protons and employing a solvent-induced shift method, the ¹H NMR spectrum containing the dithiocarbamate complexes of Co(II), Cr(VI), Ni(II) and Pb(II) is fully resolved at CDCl₃/ C₆D₆ below 40%/60%. The detection limits for Co(II), Cr(VI), Ni(II) and Pb(II) are estimated to be 0.12, 0.073, 0.11 and 0.27 μg/mL, respectively, in the sample solution. Received: 31 July 1997 / Revised: 24 October 1997 / Accepted: 31 October 1997     

Exploring Regioselective Bond Cleavage and Cross‐Coupling Reactions using a Low‐Valent Nickel Complex

Recently, esters have received much attention as transmetalation partners for cross‐coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}₂(μ‐η²:η²‐C₆H₆)] (dtbpe=1,2‐bis(di‐tert‐butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η²‐carbonyl complexes. In contrast, acetylthioesters underwent rapid C_acyl?S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross‐coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η²‐carbonyl complex, phenyl esters were found to predominantly undergo C_aryl?O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2‐naphthyl acetate was also found to undergo clean C_aryl?O bond cleavage, and although stoichiometric cross‐coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive.     

Nucleophilic substitution by arenethiolates at the carbene carbon of pentacarbonyl(methoxymethylcarbene)-metal(o) complexes (metal = Cr,Mo, or W)

The phenylthiocarbene complexes, [(CO)₅MC(CH₃)(SPh)] (M = Cr, Mo, or W) have been prepared in good yield by the reaction of [(CO)₅MC(CH₃)(OCH₃)] (M = Cr, Mo, or W) with NaSPh in benzene/methanol in the presence of HCl. A series of para-substituted phenylthiocarbene complexes of tungsten. [(CO)₅WC(CH₃)SC₆H₄Y)], (Y = p-Br, p-F, p-H, p-CH₃, p-OCH₃ or p-OH) have also been prepared by the reaction of the appropriate arenethiolate ion with [(CO)₅WC(CH₃)(OCH₃)]. Poor nucleophiles such as p-nitrobenzenethiolate and pentafluorobenzenethiolate did not react with [(CO)₅WC(CH₃)(OCH₃) to form the corresponding phenylthiocarbene complex. A mechanism accounting for the formation of these phenylthiocarbene complexes is proposed. The complexes have been characterized by their infrared, electronic, mass, ¹H NMR, and ¹³C NMR spectra. These spectroscopic data have been used to establish the structure of these complexes in solution and indicate that the phenyl ring bonded to sulfur is probably not coplanar with the “carbene” plane.